Method of preparing sheet or film material



Patented Mar. 25, 1941;

UNITED STATES METHOD OF PBEPARIN G SHEET R FILM MATERIAL Edouard M. liratnbgdcn Dunes, Ind., asslgnor to Marbon Corporation, a corporation of Delaware No Drawing.

This invention relates to a method of preparing sheet or film material for the manufacture of thin, transparent, flexible films or sheets free from impurities and pin holes for use in the l:vraipping and packaging of articles of various in s.

More specifically this invention relates to a method of preparing sheet or film material for making transparent casein sheets free from impurities and from pin holes and which will not become brittle upon aging.

. It is an object of this invention to provide a methcid of making sheet or film material having as its base a protein which is readily soluble in water or which may be rendered soluble by means of an alkaline or basic reacting substance, the

sheet or film material being characterized by its.

thinness, clear and sparkling transparency, freeness from pin holes, lack of brittleness andby its toughness.

Another object oi this invention is to provide a process for preparing sheet or film material composed of casein and free from brittleness. A specificoblect of this invention is to remove impurities from commercial casein and to prepare a film forming material free from such impurities. A a Other and further objects of this invention will become apparent from the followlng'description and accompanying claims.

The base of the mm or sheet material prepared according to this invention is a 'protein which is readily soluble in water or which may be rendered soluble by'means of an alkaline or basic as reacting substance. Examples'of suitable proteins of this type are caseins, such as may be derived from milk, soya beans and other sources. It is known that the commercial form of such casein contains certain for ingredients, in-

herent in impurities in the form of dirt, mineral salts such as, for example, calcium acetate, calcium citrate, calcium chloride and calcium phosphate and other materials.

The first step in the Drocessis the purification of the crude casein. Casein is an amphoteric substance having an 'isoelectric point of a pH value of 4.6. This means that casein forms salts with acids at any pH value numerically lower than 4.6 and also forms salts with bases at any pH value numerically greater than 4.6. Y

According to this invention the pH value of the casein is adjusted from 4.6 to 5.0 by adding an acid or a-base as required, and is then washed with water in order to remove the resultinginorganic salts and any other readily water soluble Application October Serial no. 46,495

3 Claims. (01. 106 -38) impurities. It isnot necessary to eliminate the calcium radical entirely if present in combination with casein as calcium caseinate. Thorough Washing of the casein is very essential in order' to remove all water soluble and crystalline sub- 5 stances, the present of which in the final sheet material would impart undesirable opacity .thereto due to surface crystallization and upon agilm would also render the sheet brittle.

After the casein has been properly washed with 10 water and its pH adjusted to from 4.6 to 5.0, water is added in the proportion of from 6 to 7' parts of water to 1 part of casein by weight. The casein is dissolved with a suitable basic substance capable of reacting with the casein to form a 15 water soluble compound. It hasbeen found-that various caustic alkalis, such as sodium, potassium and" lithium hydroxides, ammonium hydroxide and various organic bases, such as alkylami'nes and 'hydroxyalkylamines are suitable for this 20 purpose. As an organic basethere mayfbe used analkylamine, such as the amylamines, ethylene diamine, butylamine and the like and a hydroxyalkylamine, such as ethanolamine, viz., triethanolamine, monoethanolamine, diethanolamine, or 25 a mixturefof the mono-, diand tri-ethanolamines, or. a' polyethan'olamine; The poly-ethanolamines are produced by the action of ethylene oxide. on triethanolamine. A mixture of one or moreof the. ethanolamlnes andan alkali metal 30 hydroxide .is likewise'satisfactory. A hydroxyl- .aminemayalsobusedj.

0f the variousbasic substances mentioned above, it is preferred to use either caustic potash or triethanolamine or 'a 'mixture of the two. 35 Caustic soda has a tendency to produce films that become brittle at higher humidities than do films prepared with caustic potash or an ethanolamine. .These latter two basic substances produce filmsthat resist the embrittlingeffect of low humid- 40 ities. Itis probable that triethanolamine has itself a slight plasticizing eflect on the film.

The neutralization of the casein mass is carried out by the addition of the basic substance until the pH valueof the solution remains constant at about 6.8, at which point the casein will all be in solution as a soluble caseinate. The

.- casein may be madeto dissolve at pH values below 6.8 but it is preferred to adjust the solution to this value because there-is obtained a better reaction subsequently of the casein solution with formaldehyde when the pH value is at this point. The solution will also be satisfactory if the neutralization is continued to "a pH value of from 7 to 7.5 but if this-is done with theuse of an eth- 55 vary between 8 and 14 parts perhundred parts of casein by weight depending upon the ash content of the casein used. The ash content represents the combined calcium.

Alternatively; commercial casein may be purifiedwithout the preliminary step of adjusting its 7 pH value to between 4.6 and 5.0 and washing with water.

If desired, the commercial casein may directly be treated with a basic substance to form a water soluble compound. Commercial casein. is admixed with water in the proportion of from 6 to 7 parts of water to one part of casein by weight and the basic substance is added until the pH value of the solution remains ethylene glycol, mono-ethyl or butyl ethers, di-

constant at about 6.8 or until the pH value lies between 6.5 and 7.5. The amount of water added should be carefully regulated to prevent the .iormation of a too dilute solution which will dissolve the impurities in the casein. A concentration of 6 to 7 parts of waterto one part of casein, viz., 12.5 to 15% casein, is desirable because at this concentration the salt impurities present in commercial casein will not dissolve. The solution is then filtered through a filter medium of sufilcient s'fineness to prevent passage of the undissolved foreign particles, such as dirt or salt crystals therethrough.

If desired the alkaline casein solution prepared as described above, may be heated to temperatures between and 142 F. and agitated preferably for from four to eight hours with a suitable filter aid such as diatomaceous earth, kieselguhr or the like. This period of contact between the casein solution and the filter aid gives a high degree of clarity to the solution necessary for making a highly transparent film free from specks and blemishes.

The alkaline solution withor without the filter aid can also befiltered under pressure to speed up the separation of the undissolved impurities and salt from the dissolved casein compound.

It has been found that commercial casein having an ash content (calcium) of 2%% or less gives a very satisfactory final product. Since the a combined calcium acts as a base it is not necessary to use as much of the alkaline material in purifying the casein as would ordinarily be necessary. As much as 14 parts of triethanolamine may be required to neutralize a hundred parts of casein if the casein is substantially free from calcium. Equivalent reacting proportions of the other basic substances may be similarly employed to put the-casein in solution and produce the desired pH of the resulting alkaline solution.

A plasticizer is next added to the filtered alkaline solution in an amount equal to from 5 to 30 percent, preferably 20 percent of the ;weight It'is essential that the gums and of casein (on a dry basis used). A hygroscopic liquid such as glycerine is desirable. Polyglycerols, water soluble glycols, such as ethylene or diethylene glycol or mixtures thereof or a deli-v quescent salt, such as potassium acetate, may be used in place of all or part of the glycerine.

films or sheet material fir accordance witliknown 10 methods To the clarified and filtered solution there may be also added a number of emulsified substances for imparting certain properties to the finished sheet or film. Various natural or synthetic gums 15 and resins, with or without waxes, mineral oil and the like can be added in the form of emulsions, but it has been found that chlorinated diphenyls with gum dammar, paraffin wax and a refined ,white mineral oil are particularly satis- 2 factory. 7

Other resins such as gum rosin, and other gums'such as elemi, may be employed.

Since the gums and resins are insoluble, it is necessary to use a dispersing or emulsifying 25 agent. It is preferred to use, for this purpose, a mixture of alkali metal salts of organic solphonic acids, such as, for example Soap H3 Soap H comprises purified andneu'tralized hydrocarbonulphonic acids'obtainedlas a by-prod- 30 uct in th manufacture of whlte'..- oi1s. Triethanolamine' sulfonate can also be used as well as triethanolamine oleate or sulfonated castor oil. 5

Soap H or suifonated castor oil may also be 35 used without the addition of any resins or gums to give the solution better wetting actioigoward, iii-m7 the surface on which the forming solution is cast. The Soap H and sulfonated castor oil may vbe added either singly or together in 40 amounts up to 15% by weight of the casein (dry basis). They have a slight plasticizing action in addition to their property of lowering" the surface tension of the solution.

Before adding the resinous substances to the 45 casein solution, they are preferably melted under heat. The following illustrates thepreferred W proportions but the invention is not'to be construed as limited to the exact proportions. since obviously they may be varied: V p

Chlorinated diphenyl Soap H .I Cyclohexancl 1 From 5 to 50%, but preferably about 11% of this melted mixture, based upon the dry weight of the casein used, is added to the casein solution. The Soap H may be replaced by other suitable emulsifying agents such as those discussed above.

The resinous mixture is poured into a small quantity ofthe casein solution kept at approxior mately to F. with constant agitation,

and the resulting emulsion is then transferred to the ,main portion of the casein solution.

resins be highly dispersed in order to obtain a clear film.

To accomplish this, a large proportion of the 70 emulsifying agent is necessary. It is preferred ture when Soap H is used because cyclohexanol 7 tration of suitable proportion in forming the film material of my invention. The invention is not to be limited to these proportions and specific ingredients as other substances may be used and the proportions may be varied within considerable limits:

Preferred Broader range Parts by Parts by weight weight Protein: Casein (firmed) 600 Basic substance: lethanolamine. 50 45 to 86 Plaaticlser: Glycerine m to 180 Gums and resins:

. Chlorinated diphenyl l6 0 to 150 Gum dammar l6 0 to 150 Emulsiiying agent: Soap H 30 0 to 800 vllexalin (cyclohexanol) 6 0 to 60 The combined effect of-the gums, resins, and emulsifying agent is to give the film more body, greater brilliance, or sheen, greater strength and better resistance to low humidlties. For example, if the washed casein be dissolved with sodium hydroxide, a film is obtained which becomes brittle at approximately 35% relative humidity. The combined eflect of the resins and emulsifying agents will lower the brittle point to about 30% relative humidity, and when the preferred basic substances, potassium hydroxide or triethanolamine. are used as the dissolving agent for the casein, the resulting film will withstand relative humidities as low as 17 to 20% without becoming brittle.

In casting a composition such as described into sheets or films, a suitable insolubilizing agent, such as an aldehyde, or the like, is added. The effect of such an agent is to render the caseinate insoluble in water and to strengthen the film greatly. For this purpose, I prefer to use a 6% solution of formaldehyde in water. A stronger solution will tend to cause precipitation of the casein at the time the solutions are mixed. The preferred proportion for these solutions is about 1 part of the 6% formaldehyde solution to 25 parts by volume of the casein solution. Since this is more than sumcient formaldehyde to give the maximum insolubilizlng action, lesser quantitles of formaldehyde may therefore be used. The two solutions should be thoroughly mixed Just before use and then promptly cast in continuous films or formed into sheets, since the mixture sets in a few minutes.

It is preferable. to mix the solutions continuously in small quantities and immediately and continuously fiow the mixture onto a suitable forming belt. A belt having a coating of cellulose nitrate will be satisfactory forthis purpoge,

After being cast onto the formingor carrier belt, the film on the belt is subjected toa drying operation by passing the belt' through heated drier chambers, under controlled temperature and humidity conditions. The film is thereby dried and is then stripped from the carrier belt and wound into a roll in a continuous operation. The reaction between the casein and organic amineissimilartcthatbetweencasclnandan alkali, metal hydroxide and results in the formstion of a caseinate of the particular organic amine used. This reaction product is soluble in water. The resinous substances added, however, such as a chlorinated dlphenyl, dammar gum,

or the like, are not water soluble but may be highly dispersed in the solution of the caseinate by means of suitable dispersing and emulsifying agents. 1

Chlorinated diphenyls may be used alone or incomblnation with gums, resins or waxes. Drying oils, such as linseed or tung oil, may also material at a pH between 6.5 and 7.5 and at a concentration of casein sufiiclently great to prevent the dissolving of the impurities and salts. A concentration of about 12.5 to 15% or more of the casein is desirable. The casein solution may be admixed with a filter aid and agitated preferable -while heated to temperatures around l30 and F. The addition of a filter aid, however, is not necessary. The solution is then filtered through any suitable filter medium which will retain the undissoived particles in the solution and the filtering, operation may be effected under pressure to increase the speed of filtering.

The resulting clarified and filtered solution is then admixed with suitable plasticizers and gums as described above and may be directly fed to the casting machine for reacting with a hardening agent to produce the film or sheet material.

Having now described my invention, it is apparent that numerous details of the process may be varied through a wide range without departing from the principles of this invention and it is, therefore not purposed to limit the patent granted hereon otherwise than necessitated by the prior art.

I claim as my invention:

L-Tho method of making a composition suitable for the production of transparent, flexible sheets or films which comprises washing casein at a pH of 4.6 to 5.0 to free the from water soluble substances, reacting the purified casein in an aqueous medium with trieth'anolamine to form a solution of triethanolamine .caselnate, filtering the solution and adding a plasticizer and an insolubilizing agent to said solution.

2. The improvement in the method of making a composition suitable for the production of a transparent, flexible sheet or film from' crude casein, which comprises adjusting the pI-I value of'the casein to 4.6 to 5.0, washing with water to remove resulting inorganic salts, reacting the washed caselnin an aqueous medium with trisolution of ethanol amine caseinate.

-snousanrrxaarz. 

